CN102167786A - Method for preparing modified casein/nanometer silica composite film-forming agent through in-situ soap-free seed emulsion polymerization - Google Patents
Method for preparing modified casein/nanometer silica composite film-forming agent through in-situ soap-free seed emulsion polymerization Download PDFInfo
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Abstract
The invention belongs to the production field of a composite film-forming agent and particularly relates to a method for preparing a modified casein/nanometer silica composite film-forming agent through in-situ soap-free seed emulsion polymerization. By adopting the prior art, the formed casein film is hard and brittle, has low extensibility and poor water resistance and is easy to mildew and crack; and pure casein can not meet the industrial demands. The method uses natural protein casein molecule as main chain; and the branched chain is acrylic graft copolymer with an active reactive end group. Therefore, the modified casein has the excellent characteristics of both protein film-forming agent and acrylic resin film-forming agent and is characterized by high adhesive force, high temperature resistance, good air permeability, high water resistance, excellent mechanical properties and the like; and by introducing a defined amount of nanometer silica, the nano-effect of nanometer silica can be shown and the mechanical properties or color development property of the product can be increased to a certain extent. When the composite film-forming agent is used for leather finishing, the coating can have excellent hygienic property, natural glossiness, higher dry rubbing resistance and mechanical properties and dry hand feeling.
Description
Technical field
The invention belongs to the compound film former production field, being specifically related to a kind of original position does not have the method that the soap seed emulsion polymerization prepares modified Casein/nano silicon compound film former.
Background technology
Environmental pollution exhausted day by day along with petroleum resources and that non-degraded synthesized polymer material causes is serious day by day, and the development and utilization of renewable resources and environment-friendly material receives concern more and more widely, and has classified one of international front subject field as.Casein is as a kind of natural polymer, bounding force is preferably arranged, anti-flatiron, anti-polishing, high temperature resistant, casein solution has good stably dispersing and levelling effect to pigment, certain film forming properties is arranged again, and be a kind of renewable starting material of fully biodegradable.Casein was used till today from nineteen twenty, occupied extremely important status in tanning industry always, but because self structure, the casein film forming is crisp firmly, and extensibility is little, and poor water resistance is easily mouldy, split slurry, and simple casein can not satisfy the needs of industry.The casein side chain have carboxyl (COOH), amino (NH2) and hydroxyl (functional group such as OH), in the presence of initiator, can introduce various monomers it is carried out modification, casein is endowed good performance through a series of modification meetings, and is applied to fields such as leather, papermaking, packing as membrane-forming agent.[Wang?N?G,?Zhang?L,?Lu?Y?S,?et?al.?Properties?of?crosslinked?casein/water-borne?polyurethane?composites[J].
J.?Appl．Polym?Sci，2004，91：332-338；Dong?Q?Z，Gu?L?X．Synthesis?of?AN-g-casein?copolymer?in?concentratec?aqueous?solution?of?sodium?thiocyanate?and?AN-g-casein?fiber’s?structure?and?property?[J].?Eur?Polymer?J,?2002,?38：511-519；Pan，X.．Micellization?of?Casein-graft-Dextran?Copolymer?Prepared?through?Maillard?Reaction[J]，Bio?Polymers?-New?York，2006，?81(1)：29-38；N.Somanathan?,etal．
Syhthesis of Casein Graft Poly (acrylonitrile)) [J] .Polymer.J, 1993,25 (9): 939-946.] inorganic nano-particle and modified Casein is compound, can prepare eco-friendly biodegradation type casein based nano composite material, at present, the also rarely seen report of this aspect research.[Tassawuth?Pojanavaraphan,?Rathanawan?Magaraphan,?Bor-Sen?Chiou．Development?of?Biodegradable?Foamlike?Materials?Based?on?Casein?and?Sodium?Montmorillonite?Clay?[J].?Biomacromolecules?,2010,?11:?2640–2646]。
Summary of the invention
The purpose of this invention is to provide simple, renewable, the environment amenable employing original position of a kind of technology and do not have the method that the soap seed emulsion polymerization prepares modified Casein/nano silicon compound film former.
For achieving the above object, the technical solution used in the present invention is:
A kind of original position that adopts does not have the method that the soap seed emulsion polymerization prepares modified Casein/nano silicon compound film former, and its special character is: preparation method's step that described no soap seed emulsion polymerization prepares modified Casein/nano silicon compound film former is as follows:
(1) preparation of casein lysate
Getting mass fraction is that 2.1～8.4 parts casein food grade, 0.525～2.1 part of trolamine and 33～83 parts of deionized waters add in the there-necked flask, makes the casein dissolving by regulating water-bath temperature regulating device regulation system temperature, stirring, and promptly gets the casein lysate.
(2) preparation of hexanolactam modified Casein liquid
The preparation mass fraction is 4.0～16.0 parts of 25% caprolactam water solutions; The regulation system temperature drips caprolactam water solution, waits to dropwise, and continues insulation, gets hexanolactam modified Casein liquid;
(3) preparation of modified Casein/nano silicon compound film former
Get mass fraction and be 0.6～2.4 part nano silicon, the adding system also stirs; Take by weighing 1/2 and mix acrylic monomer [1.11～4.44 parts of methyl methacrylates (MMA), 0.2～0.8 part of butyl acrylate (BA), 0.2～0.8 part of vinyl acetate (VAC)], the system of pouring into stirs and makes its emulsification, obtains seed emulsion; The preparation massfraction is 9.09～36.36 parts of 1% initiator solutions; Above-mentioned initiator solution and residue 1/2 mix monomer are added dropwise to reaction system simultaneously; Wait to dropwise, the regulation system temperature continues insulation reaction; System is reduced to room temperature then, and adding an amount of mass percent is 30% ammoniacal liquor, in and system be 7.8～8.2 to pH, promptly get original position does not have modified Casein/nano silicon compound film former that the soap seed emulsion polymerization prepares.
In the preparation of the casein lysate of above-mentioned steps (1), hydrolysis temperature is 65 ℃～70 ℃, and the hydrolysis churning time is 120～150 minutes.
In the preparation of the hexanolactam modified Casein liquid of above-mentioned steps (2), the system temperature of reaction is 75 ℃～80 ℃, and after the dropping caprolactam water solution finished, continuing the insulation reaction time was 240～300 minutes.
In the preparation of the modified Casein of above-mentioned steps (3)/nano silicon compound film former, churning time is 60～90 minutes after the nano silicon adding system; Mixing the acrylic monomer adding system stirring and emulsifying time is 20～25 minutes; The dropping time of initiator solution and mix monomer should be less than 30 minutes, dropwises, and the regulation system temperature is 80～85 ℃, and continuing the insulation reaction time is 120～180 minutes.
The present invention compares with respect to prior art, have following advantage: the present invention is a main raw material with natural degradable protein material casein and acrylic monomer cheap and easy to get, and introduce proper amount of nano silicon-dioxide, adopt original position not have the soap seed emulsion polymerization and prepare modified Casein/nano silicon compound film former.According to said method Zhi Bei modified Casein/nano silicon compound film former is applied to leather finish, and the coating sanitation performance is good, the glossiness nature, and anti-xerotripsis, fastness and mechanical mechanics property excellence and feel are dry and comfortable.This membrane-forming agent has concurrently natural and advantage synthesized polymer material, is a kind of excellent property, environment amenable membrane-forming agent, also can be applicable to ink vehicle.
Embodiment
Following the present invention will be further described in conjunction with specific embodiments, but protection scope of the present invention is not limited in this:
Embodiment 1:
Getting mass fraction is that 2.1 parts casein food grade, 0.525 part of trolamine and 83 parts of deionized waters add in the there-necked flask, regulate the water-bath temperature regulating device, make temperature reach 68 ℃ of set(ting)values, strict control solvent temperature (68 ℃), treat that casein dissolving back keeps stirring 140 minutes, promptly gets the casein lysate.Get mass fraction and be 0.9 part hexanolactam, add in 3.6 parts the deionized water, evenly stirring and obtaining mass fraction is 25% caprolactam water solution; Regulate temperature regulating device and treat that temperature reaches 78 ℃, drip caprolactam water solution, wait to dropwise, continued insulation reaction 280 minutes, promptly get hexanolactam modified Casein liquid.Get mass fraction and be 0.6 part nano silicon, the adding system also stirred 80 minutes; Take by weighing 1/2 and mix acrylic monomer [1.11 parts of methyl methacrylates (MMA), 0.2 part of butyl acrylate (BA), 0.2 part of vinyl acetate (VAC)], the system of pouring into stirs and makes its emulsification 23 minutes, obtains seed emulsion; After getting massfraction and be the deionized water that 0.09 part ammonium persulphate is dissolved in 9 parts, stir, obtain massfraction and be 1% initiator solution; Above-mentioned initiator solution and residue 1/2 mix monomer [1.11 parts of methyl methacrylates (MMA), 0.2 part of butyl acrylate (BA), 0.2 part of vinyl acetate (VAC)] are respectively added a dropping funnel and be added dropwise to system simultaneously, dripped off in 30 minutes; Wait to dropwise, regulate temperature regulating device and treat that temperature reaches 84 ℃, insulation reaction 160 minutes.Reduce to room temperature, adding an amount of mass percent is in 30% ammoniacal liquor and system is 7.8 to pH, and promptly getting original position does not have modified Casein/nano silicon compound film former that the soap seed emulsion polymerization prepares.
Embodiment 2:
Getting mass fraction is that 4.2 parts casein food grade, 1.05 parts of trolamines and 66 parts of deionized waters add in the there-necked flask, regulate the water-bath temperature regulating device, make temperature reach 66 ℃ of set(ting)values after, strict control solvent temperature (66 ℃), treat that casein dissolving back keeps stirring 130 minutes, promptly gets the casein lysate.Get mass fraction and be 1.8 parts hexanolactam, add in 7.2 parts the deionized water, evenly stirring and obtaining mass fraction is 25% caprolactam water solution; Regulate temperature regulating device and treat that temperature reaches 78 ℃, drip caprolactam water solution, wait to dropwise, continued insulation reaction 260 minutes, promptly get hexanolactam modified Casein liquid.Get mass fraction and be 1.2 parts nano silicon, the adding system also stirred 80 minutes; Take by weighing 1/2 and mix acrylic monomer [2.22 parts of methyl methacrylates (MMA), 0.4 part of butyl acrylate (BA), 0.4 part of vinyl acetate (VAC)], the system of pouring into stirs and makes its emulsification 22 minutes, obtains seed emulsion; After getting massfraction and be the deionized water that 0.18 part ammonium persulphate is dissolved in 18 parts, stir, obtain massfraction and be 1% initiator solution; Above-mentioned initiator solution is mixed acrylic monomer [2.22 parts of methyl methacrylates (MMA) with residue 1/2,0.4 part of butyl acrylate (BA), 0.4 part of vinyl acetate (VAC)] respectively add a dropping funnel and be added dropwise to system simultaneously, dripped off in 30 minutes; Wait to dropwise, regulate temperature regulating device and treat that temperature reaches 82 ℃, insulation reaction 150 minutes.Reduce to room temperature, adding an amount of mass percent is in 30% ammoniacal liquor and system is 8.0 to pH, and promptly getting original position does not have modified Casein/nano silicon compound film former that the soap seed emulsion polymerization prepares.
Embodiment 3:
Getting mass fraction is that 6.3 parts casein food grade, 1.575 parts of trolamines and 49 parts of deionized waters add in the there-necked flask, regulate the water-bath temperature regulating device, make temperature reach 70 ℃ of set(ting)values after, strict control solvent temperature (70 ℃), treat that casein dissolving back keeps stirring 150 minutes, promptly gets the casein lysate.Get mass fraction and be 2.7 parts hexanolactam, add in 10.8 parts the deionized water, evenly stirring and obtaining mass fraction is 25% caprolactam water solution; Regulate temperature regulating device and treat that temperature reaches 80 ℃, drip caprolactam water solution, wait to dropwise, continued insulation reaction 300 minutes, promptly get hexanolactam modified Casein liquid.Get mass fraction and be 1.8 parts nano silicon, the adding system also stirred 90 minutes; Take by weighing 1/2 and mix acrylic monomer [3.33 parts of methyl methacrylates (MMA), 0.6 part of butyl acrylate (BA), 0.6 part of vinyl acetate (VAC)], the system of pouring into stirs and makes its emulsification 25 minutes, obtains seed emulsion; After getting massfraction and be the deionized water that 0.27 part ammonium persulphate is dissolved in 27 parts, stir, obtain massfraction and be 1% initiator solution; Above-mentioned initiator solution is mixed acrylic monomer [3.33 parts of methyl methacrylates (MMA) with residue 1/2,0.6 part of butyl acrylate (BA), 0.6 part of vinyl acetate (VAC)] respectively add a dropping funnel and be added dropwise to system simultaneously, dripped off in 30 minutes; Wait to dropwise, regulate temperature regulating device and treat that temperature reaches 85 ℃, insulation reaction 180 minutes.Reduce to room temperature, adding an amount of mass percent is in 30% ammoniacal liquor and system is 8.2 to pH, and promptly getting original position does not have modified Casein/nano silicon compound film former that the soap seed emulsion polymerization prepares.
Embodiment 4:
Getting mass fraction is that 8.4 parts casein food grade, 2.1 parts of trolamines and 33 parts of deionized waters add in the there-necked flask, regulate the water-bath temperature regulating device, make temperature reach 65 ℃ of set(ting)values after, strict control solvent temperature (65 ℃), treat that casein dissolving back keeps stirring 120 minutes, promptly gets the casein lysate.Get mass fraction and be 3.6 parts hexanolactam, add in 12.4 parts the deionized water, evenly stirring and obtaining mass fraction is 25% caprolactam water solution; Regulate temperature regulating device and treat that temperature reaches 75 ℃, drip caprolactam water solution, wait to dropwise, continued insulation reaction 240～300 minutes, promptly get hexanolactam modified Casein liquid.Get mass fraction and be 2.4 parts nano silicon, the adding system also stirred 60 minutes; Take by weighing 1/2 and mix acrylic monomer [4.44 parts of methyl methacrylates (MMA), 0.8 part of butyl acrylate (BA), 0.8 part of vinyl acetate (VAC)], the system of pouring into stirs and makes its emulsification 20 minutes, obtains seed emulsion; After getting massfraction and be the deionized water that 0.36 part ammonium persulphate is dissolved in 36 parts, stir, obtain massfraction and be 1% initiator solution; Above-mentioned initiator solution is mixed acrylic monomer [4.44 parts of methyl methacrylates (MMA), 0.8 part of butyl acrylate (BA), 0.8 part of vinyl acetate (VAC)] respectively add a dropping funnel and dropping simultaneously with residue 1/2, dripped off in 30 minutes; Wait to dropwise, regulate temperature regulating device and treat that temperature reaches 80 ℃, insulation reaction 120 minutes.Reduce to room temperature, adding an amount of mass percent is in 30% ammoniacal liquor and system is 8.1 to pH, and promptly getting original position does not have modified Casein/nano silicon compound film former that the soap seed emulsion polymerization prepares.
The product main chain is a natural protein casein molecular backbone chain among the present invention, its side chain is the acrylic acid or the like graft copolymer with active reaction end group, therefore, modified Casein has the excellent specific property of protein-based membrane-forming agent and crylic acid resin membrane-forming agent concurrently, it is strong to have cohesive force, and high temperature resistant, good permeability, water tolerance reach characteristics such as mechanical property excellence by force, simultaneously, the an amount of introducing of nano silicon can be brought into play its nano effect, improves the mechanical mechanics property of product or color developing etc. to a certain extent.This product is used for leather finish can gives the sanitation performance of coating excellence, the glossiness of nature, higher anti-xerotripsis fastness and mechanical mechanics property and dry and comfortable feel.Therefore modified Casein/nano silicon the compound film former that adopts original position not have the preparation of soap seed emulsion polymerization has concurrently natural and advantage synthesized polymer material, is a kind of excellent property, environment amenable material.
Claims (5)
1. one kind is adopted original position not have the method that the soap seed emulsion polymerization prepares modified Casein/nano silicon compound film former, and its special character is: preparation method's step that described no soap seed emulsion polymerization prepares modified Casein/nano silicon compound film former is as follows:
(1) preparation of casein lysate
Getting mass fraction is that 2.1～8.4 parts casein food grade, 0.525～2.1 part of trolamine and 33～83 parts of deionized waters add in the there-necked flask, makes the casein dissolving by regulating water-bath temperature regulating device regulation system temperature, stirring, and promptly gets the casein lysate;
(2) preparation of hexanolactam modified Casein liquid
The preparation mass fraction is 4.0～16.0 parts of 25% caprolactam water solutions; The regulation system temperature drips caprolactam water solution, waits to dropwise, and continues insulation, gets hexanolactam modified Casein liquid;
(3) preparation of modified Casein/nano silicon compound film former
Get mass fraction and be 0.6～2.4 part nano silicon, the adding system also stirs; Take by weighing 1/2 and mix acrylic monomer, the system of pouring into stirs and makes its emulsification, obtains seed emulsion; The preparation massfraction is 9.09～36.36 parts of 1% initiator solutions; Above-mentioned initiator solution and residue 1/2 mix monomer are added dropwise to reaction system simultaneously; Wait to dropwise, the regulation system temperature continues insulation reaction; System is reduced to room temperature then, and adding an amount of mass percent is 30% ammoniacal liquor, in and system be 7.8～8.2 to pH, promptly get original position does not have modified Casein/nano silicon compound film former that the soap seed emulsion polymerization prepares.
2. employing original position according to claim 1 does not have the method that the soap seed emulsion polymerization prepares modified Casein/nano silicon compound film former, it is characterized in that: in the preparation of the casein lysate of described step (1), hydrolysis temperature is 65 ℃～70 ℃, and the hydrolysis churning time is 120～150 minutes.
3. employing original position according to claim 1 and 2 does not have the method that the soap seed emulsion polymerization prepares modified Casein/nano silicon compound film former, it is characterized in that: described step (2) system temperature of reaction is 75 ℃～80 ℃, after the dropping caprolactam water solution finished, continuing the insulation reaction time was 240～300 minutes.
4. employing original position according to claim 3 does not have the method that the soap seed emulsion polymerization prepares modified Casein/nano silicon compound film former, it is characterized in that: in the described step (3), described churning time is 60～90 minutes; The stirring and emulsifying time is 20～25 minutes; The dropping time is less than 30 minutes, dropwises, and the regulation system temperature is 80～85 ℃, and continuing the insulation reaction time is 120～180 minutes.
5. there is not the method that the soap seed emulsion polymerization prepares modified Casein/nano silicon compound film former according to claim 2 or 4 described employing original positions, it is characterized in that: described mixing acrylic monomer is 1.11～4.44 parts of methyl methacrylates, 0.2～0.8 part of butyl acrylate, 0.2～0.8 part of vinyl acetate.
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| CN102935235A (en) * | 2012-11-22 | 2013-02-20 | 陕西科技大学 | Preparation method of modified casein drug-carrying controlled-release thin film |
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